Spacer groups for functionalized resins in tires

ABSTRACT

This invention relates to a functionalized resin composition having the formula P—S—X where S is a spacer selected from at least one of C 2 -C 40  straight chain and branched alkyl, C 6 -C 40  aromatics, butadiene, isoprene, and combinations thereof, P is a polymer backbone selected from at least one of dicyclopentadiene (DCPD)-based polymers, cyclopentadiene (CPD)-based polymers, DCPD-styrene copolymers, C 5  homopolymers and copolymer resins, C 5 -styrene copolymer resins, terpene homopolymer or copolymer resins, pinene homopolymer or copolymer resins, C 9  homopolymers and copolymer resins, C 5 /C 9  copolymer resins, alpha-methylstyrene homopolymer or copolymer resins, and combinations thereof, and X is a silane.

CROSS REFERENCE TO RELATED APPLICATION

This application is a National Stage Application of InternationalApplication No. PCT/US2015/019170, filed Mar. 6, 2015, and claimspriority to U.S. Provisional Patent Application No. 61/972,970, filedMar. 31, 2014, the disclosures of which are fully incorporated herein byreference in their entireties.

FIELD OF THE INVENTION

This invention relates to the use of a spacer group between a resinmolecule and a reactive functional group for use in tire compoundapplications.

BACKGROUND

Treads of high performance tires are expected to have outstandingtraction and handling properties. Generally, tire treads are compoundedwith high filler loading and resins to achieve these desired properties.

For passenger tires, miscible resins are typically used in treadcompound formulations in order to increase traction characteristics.Although these resins increase overall traction, tread compoundsformulated with these miscible resins tend to suffer from reducedtraction and handling at high speeds or at high internal tire generatedtemperatures during hard driving.

The problems observed in passenger tires at high speeds and temperatureshave been solved by adding high softening point immiscible resins andresin blends to tread compounds for use in race car tires. For instance,it has been observed that using resin packages with high G′ (storagemodulus) values at high temperatures along with high tangent delta(ratio of loss modulus to storage modulus) values improve tireperformance at high speeds and temperatures. However, since addingimmiscible resins reduces the life of the tire tread, using immiscibleresins for high performance passenger tires is not a viable optionbecause of the increased stability and lifetime requirements ofpassenger tires versus those of race car tires.

Patent Application No. PCT/US2014/050475 discloses DCPD-basedfunctionalized resins prepared via metathesis chemistry. There stillremains a need for a resin that demonstrates improved durability alongwith improved traction and handling in a cost effective manner.

SUMMARY OF THE INVENTION

The foregoing and/or other challenges are addressed by the methods andproducts disclosed herein.

This invention relates to a functionalized resin composition having theformula P—S—X where S is a spacer selected from at least one of C₂-C₄₀straight chain and branched alkyl, C₆-C₄₀ aromatics, butadiene,isoprene, and combinations thereof, P is a polymer backbone selectedfrom at least one of dicyclopentadiene (DCPD)-based polymers,cyclopentadiene (CPD)-based polymers, DCPD-styrene copolymers, C₅homopolymers and copolymer resins, C₅-styrene copolymer resins, terpenehomopolymer or copolymer resins, pinene homopolymer or copolymer resins,C₉ homopolymers and copolymer resins, C₅/C₉ copolymer resins,alpha-methylstyrene homopolymer or copolymer resins, and combinationsthereof, and X is a silane.

This invention further relates to a tire tread composition comprising(i) a functionalized resin composition within the range from 5 to 100phr; (ii) 100 phr of a diene elastomer; and (iii) an inorganic fillerwithin the range from 50 to 150 phr; wherein the functionalized resincomposition has the formula P—S—X where S is a spacer selected from thegroup consisting of C₂-C₄₀ straight chain and branched alkyl, C₆-C₄₀aromatics, butadiene, isoprene, and combinations thereof, P is a polymerbackbone, and X is a silane.

DETAILED DESCRIPTION

Various specific embodiments of the invention will now be described,including preferred embodiments and definitions that are adopted hereinfor purposes of understanding the claimed invention. While theillustrative embodiments have been described with particularity, it willbe understood that various other modifications will be apparent to andcan be readily made by those skilled in the art without departing fromthe spirit and scope of the invention. For determining infringement, thescope of the “invention” will refer to any one or more of the appendedclaims, including their equivalents and elements or limitations that areequivalent to those that are recited.

The inventors have discovered that preparing a functionalizedhydrocarbon resin with groups capable of reacting with silica or carbonblack and introducing a spacer group between the resin molecule and thereactive functional group results in advantageous properties for theresin for use in elastomeric compounds of high performance tireapplications.

The term “phr” means parts per hundred parts of rubber, and is a measurecommon in the art wherein components of a composition are measuredrelative to the total of all of the elastomer (rubber) components. Thetotal phr or parts for all rubber components, whether one, two, three,or more different rubber components is present in a given recipe isalways defined as 100 phr. All other non-rubber components are ratioedagainst the 100 parts of rubber and are expressed in phr.

The term “interpolymer” means any polymer or oligomer having a numberaverage molecular weight of 500 or more prepared by the polymerizationor oligomerization of at least two different monomers, includingcopolymers, terpolymers, tetrapolymers, etc. As used herein, referenceto monomers in an interpolymer is understood to refer to theas-polymerized and/or as-derivatized units derived from that monomer.The terms polymer and interpolymer are used broadly herein and in theclaims to encompass higher oligomers having a number average molecularweight (Mn) equal to or greater than 500, as well as compounds that meetthe molecular weight requirements for polymers according to classic ASTMdefinitions.

All resin component percentages listed herein are weight percentages,unless otherwise noted. “Substantially free” of a particular componentin reference to a composition is defined to mean that the particularcomponent comprises less than 0.5 wt % in the composition, or morepreferably less than 0.25 wt % of the component in the composition, ormost preferably less than 0.1 wt % of the component in the composition.

The term “elastomer,” as used herein, refers to any polymer orcombination of polymers consistent with the ASTM D1566 definition,incorporated herein by reference. As used herein, the term “elastomer”may be used interchangeably with the term “rubber.”

Functionalized Resin

The functionalized resin molecules of the present invention are preparedvia metathesis methods known in the art.

Polymer Backbone

The phrase “polymer backbone” includes units derived from substituted orunsubstituted cyclopentadiene homopolymer or copolymer resins (referredto as CPD), dicyclopentadiene homopolymer or copolymer resins (referredto as DCPD or (D)CPD), terpene homopolymer or copolymer resins, pinenehomopolymer or copolymer resins, C₅ fraction homopolymer or copolymerresins, C₉ fraction homopolymer or copolymer resins, alpha-methylstyrenehomopolymer or copolymer resins, and combinations thereof. The polymerbackbone may further include units derived from (D)CPD/vinylaromaticcopolymer resins, (D)CPD/terpene copolymer resins, terpene/phenolcopolymer resins, (D)CPD/pinene copolymer resins, pinene/phenolcopolymer resins, (D)CPD/C₅ fraction copolymer resins, (D)CPD/C₉fraction copolymer resins, terpene/vinylaromatic copolymer resins,terpene/phenol copolymer resins, pinene/vinylaromatic copolymer resins,pinene/phenol copolymer resins, C₅ fraction/vinylaromatic copolymerresins, and combinations thereof. The term “resin molecule” or “resin”as used herein is interchangeable with the phrase “polymer backbone.”

The phrase “units derived from dicyclopentadiene” includes units derivedfrom substituted DCPD such as methyl DCPD or dimethyl DCPD.

Preferably, the polymer comprising units derived from dicyclopentadiene(also referred to as the “DCPD polymer”) have an Mw within the rangefrom 150 to 10,000 g/mol (as determined by GPC), more preferably from200 to 5,000 g/mol, most preferably from 300 to 1000 g/mol. Whilereference is made to a DCPD polymer, any polymer backbone comprised ofunits mentioned herein is suitable for the present invention.

Preferably, the polymer backbone comprises up to 100 mol % units derivedfrom dicyclopentadiene, more preferably within the range from 5 to 90mol % units derived from DCPD, most preferably from 5 to 70 mol % unitsderived from DCPD.

Preferably, the polymer backbone is made from a monomer mixturecomprising up to 15% piperylene components, up to 15% isoprenecomponents, up to 15% amylene components, up to 20% indene components,within the range from 60% to 100% cyclic components, and up to 20%styrenic components by weight of the monomers in the monomer mix.

Cyclic components are generally a distillate cut or synthetic mixture ofC₅ and C₆ to C₁₅ cyclic olefins, diolefins, and dimers, co-dimers andtrimers, etc., from a distillate cut. Cyclics include, but are notlimited to, cyclopentene, cyclopentadiene, DCPD, cyclohexene,1,3-cycylohexadiene, and 1,4-cyclohexadiene. A preferred cyclic iscyclopentadiene. The DCPD may be in either the endo or exo form. Thecyclics may or may not be substituted. Preferred substituted cyclicsinclude cyclopentadienes and DCPD substituted with a C₁ to C₄₀ linear,branched, or cyclic alkyl group, preferably one or more methyl groups.Preferably, the cyclic components are selected from the group consistingof: cyclopentadiene, cyclopentadiene dimer, cyclopentadiene trimer,cyclopentadiene-C₅ co-dimer, cyclopentadiene-piperylene co-dimer,cyclopentadiene-C₄ co-dimer, cyclopentadiene-methyl cyclopentadieneco-dimer, methyl cyclopentadiene, methyl cyclopentadiene dimer, andmixtures thereof.

Preferably, the polymer backbone has a refractive index greater than1.5.

Preferably, the polymer backbone has a softening point of 80° C. or more(Ring and Ball, as measured by ASTM E-28) more preferably from 80° C. to150° C., most preferably 100° C. to 150° C.

Preferably, the polymer backbone has a glass transition temperature (Tg)(as measured by ASTM E 1356 using a TA Instruments model 2920 machine)of from −30° C. to 100° C.

Preferably, the polymer backbone has a Brookfield Viscosity (ASTMD-3236) measured at the stated temperature (typically from 120° C. to190° C.) using a Brookfield Thermosel viscometer and a number 27 spindleof 50 to 25,000 mPa·s at 177° C.

Preferably, the polymer backbone comprises olefinic unsaturation, e.g.,at least 1 mol % olefinic hydrogen, based on the total moles of hydrogenin the interpolymer as determined by ¹H-NMR. Alternatively, the polymerbackbone comprises from 1 to 20 mol % aromatic hydrogen, preferably from2 to 15 mol % aromatic hydrogen, more preferably from 2 to 10 mol %aromatic hydrogen, preferably at least 8 mol % aromatic hydrogen, basedon the total moles of hydrogen in the polymer.

Preferably, the polymer backbone comprises aDCPD polymer as described inInternational Patent Application No. WO 2012/050658 A1.

Examples of polymer backbones useful in this invention include Escorez®8000 series resins sold by ExxonMobil Chemical Company in Baton Rouge,La. Further examples of polymer backbones useful in this inventioninclude Arkon® series resins sold by Arakawa Europe in Germany. Yet moreexamples of polymer backbones useful in this invention include theEastotac® series of resins sold by Eastman Chemical Company in Longview,Tex.

In the present invention, the polymer backbone is represented by theterm “P” in the formula P—S—X as described herein.

Silane

As used herein, the term “silane” means any silicon analog of asubstituted or unsubstituted hydrocarbon. The term “silane structure”refers to any compound, moiety or group containing a tetravalent siliconatom.

In the present invention, the silane is represented by the term “X” inthe formula P—S—X as described herein.

Spacer

As used herein, the term “spacer” or “spacer group” is meant to refer toany chemical group that bridges the resin molecule P and the functionalgroup X. In certain embodiments, the spacer can be an alkane, alkene, oralkyene. In certain embodiments, the spacer is branched orstraight-chained. In certain embodiments, the spacer can containfunctional groups. In embodiments, the spacer is selected from the groupconsisting of C₂-C₄₀ straight chain and branched alkyl, C₆-C₄₀aromatics, butadiene, isoprene, and combinations thereof.

Preferably, the silane with the spacer useful herein is represented byeither of the following formulae (I):

where each Y is independently a nitrogen, oxygen, or sulfur atom, each Zis independently a boron, nitrogen, oxygen, silicon, or sulfur atom,each R (representing the spacer S) is independently a monovalent (forthe first formula of I) or a divalent (for the second formula of I)substituted or unsubstituted alkyl or aromatic group of from 1 to 20carbon atoms containing at least one olefinic group, each R¹ isindependently a hydrogen atom, or a substituted or unsubstituted alkylor aromatic group of from 1 to 20 carbon atoms, each R² is independentlya divalent substituted or unsubstituted alkyl or aromatic group of from1 to 20 carbon atoms, each R³ is independently a hydrogen atom, ahalogen atom, a substituted or unsubstituted alkyl or aromatic group offrom 1 to 20 carbon atoms, R¹, R², and R³ may form single ormultinuclear rings with each other, where a-f are independently integersof 1, 2, or 3, with the proviso that a+b+c and d+e+f are both equal to3, and where independently for each Y and Z, if Z is a boron atom, thenx=2, if Y or Z is a nitrogen atom, then x=2, if Y or Z is an oxygen atomor sulfur atom, then x=1, if Z is a silicon atom, then x=3

In the present invention, the spacer group is represented by the term“S” in the formula P—S—X as described herein.

Alkene Metathesis Catalysts

An alkene metathesis catalyst is a compound that catalyzes the reactionbetween a first olefin with a second olefin to produce a product,typically with the elimination of ethylene.

Preferably, the alkene metathesis catalyst useful herein is representedby the following formula (II):

wherein, M is a Group 8 metal, preferably Ru or Os, preferably Ru; X²and X³ are, independently, any anionic ligand, preferably a halogen(preferably chlorine), an alkoxide or a triflate, or X² and X³ may bejoined to form a dianionic group and may form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms; L and L¹ are, independently, a neutral two electrondonor, preferably a phosphine or a N-heterocyclic carbene, L and L¹ maybe joined to form a single ring of up to 30 non-hydrogen atoms or amultinuclear ring system of up to 30 non-hydrogen atoms; L and X² may bejoined to form a multidentate monoanionic group and may form a singlering of up to 30 non-hydrogen atoms or a multinuclear ring system of upto 30 non-hydrogen atoms; L¹ and X³ may be joined to form a multidentatemonoanionic group and may form a single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms; R₅and R₆ are, independently, hydrogen or C₁ to C₃₀ substituted orunsubstituted hydrocarbyl (preferably a C₁ to C₃₀ substituted orunsubstituted alkyl or a substituted or unsubstituted C₄ to C₃₀ aryl);R₆ and L¹ or X³ may be joined to form a single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms; and R₅ and L or X² may be joined to form a singlering of up to 30 non-hydrogen atoms or a multinuclear ring system of upto 30 non-hydrogen atoms.

Preferred alkoxides include those where the alkyl group is a phenol,substituted phenol (where the phenol may be substituted with up to 1, 2,3, 4, or 5 C₁ to C₁₂ hydrocarbyl groups) or a C₁ to C₁₀ hydrocarbyl,preferably a C₁ to C₁₀ alkyl group, preferably methyl, ethyl, propyl,butyl, or phenyl.

Preferred triflates are represented by the following formula (III):

wherein, R₇ is hydrogen or a C₁ to C₃₀ hydrocarbyl group, preferably aC₁ to C₁₂ alkyl group, preferably methyl, ethyl, propyl, butyl, orphenyl.

Preferred N-heterocyclic carbenes are represented by the followingformulae (IV):

where each R₈ is independently a hydrocarbyl group or substitutedhydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl,propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl,hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl,cyclododecyl, mesityl, adamantyl, phenyl, benzyl, tolulyl, chlorophenyl,phenol, substituted phenol, or CH₂C(CH₃)₃; and each R₉ is hydrogen, ahalogen, or a C₁ to C₁₂ hydrocarbyl group, preferably hydrogen, bromine,chlorine, methyl, ethyl, propyl, butyl, or phenyl.

Alternatively, one of the N groups bound to the carbene in formulae (IV)is replaced with an S, O, or P atom, preferably an S atom.

Other useful N-heterocyclic carbenes include the compounds described inHermann, W. A. Chem. Eur. J., 1996, 2, pp. 772 and 1627; Enders, D. etal., Angew. Chem. Int. Ed., 1995, 34, p. 1021; Alder R. W., Angew. Chem.Int. Ed., 1996, 35, p. 1121; and Bertrand, G. et al., Chem. Rev., 2000,100, p. 39.

Preferably, the alkene metathesis catalyst used in the present inventionis one or more oftricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][3-phenyl-1H-inden-1-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[3-phenyl-1H-inden-1-ylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazol-2-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][(phenylthio)methylenel]ruthenium(II)dichloride,bis(tricyclohexylphosphine)-3-phenyl-1H-inden-1-ylideneruthenium(II)dichloride,1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)dichloride, and[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II)chloride. More preferably, the catalyst is1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyephenyl]methyleneruthenium(II)dichloride and/ortricyclohexylphosphine[3-phenyl-1H-inden-1-ylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene]ruthenium(II)dichloride.

Functionalization Process

The reactants (including the polymer backbone P) are typically combinedin a reaction vessel at a temperature of 20° C. to 200° C. (preferably50° C. to 160° C., preferably 60° C. to 140° C.) and a pressure of 0 to1000 MPa (preferably 0.5 to 500 MPa, preferably 1 to 250 MPa) for aresidence time of 0.5 seconds to 10 hours.

Preferably, within the range from 0.00001 to 1.0 moles, more preferably0.0001 to 0.05 moles, most preferably 0.0005 to 0.01 moles of catalystare charged to the reactor per mole of polymer P charged.

Preferably, within the range from 0.01 to 10 moles of silane X, morepreferably 0.05 to 5.0 moles, most preferably from 0.5 to 2.0 moles ofsilane are charged to the reactor per mole of polymer P charged.

The functionalization process is preferably a solution process, althoughit may be a bulk or high pressure process. Homogeneous processes arepreferred. (A homogeneous process is defined to be a process where atleast 90 wt % of the product is soluble in the reaction media.) A bulkhomogeneous process is particularly preferred. (A bulk process isdefined to be a process where reactant concentration in all feeds to thereactor is 70 vol % or more.) Alternately, no solvent or diluent ispresent or added in the reaction medium, (except for the small amountsused as the carrier for the catalyst or other additives, or amountstypically found with the reactants; e.g., propane in propylene).

Suitable diluents/solvents for the functionalization process includenon-coordinating, inert liquids. Examples include straight andbranched-chain hydrocarbons, such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof such as can be found commercially (Isopar™); perhalogenatedhydrocarbons, such as perfluorinated C₄ to C₁₀ alkanes, chlorobenzene,and aromatic and alkyl-substituted aromatic compounds such as benzene,toluene, mesitylene, and xylene. In a preferred embodiment, aliphatichydrocarbon solvents are preferred, such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof. In another embodiment, the solvent is not aromatic, preferablyaromatics are present in the solvent at less than 1 wt %, preferably at0.5 wt %, preferably at 0 wt % based upon the weight of the solvents.

Alternatively, the functionalization process is a slurry process. Asused herein the term “slurry polymerization process” means apolymerization process where a supported catalyst is employed andmonomers are polymerized on the supported catalyst particles. At least95 wt % of polymer products derived from the supported catalyst are ingranular form as solid particles (not dissolved in the diluent).

Preferably, the feed concentration for the functionalization process is60 vol % solvent or less, more preferably 40 vol % or less, mostpreferably 20 vol % or less.

The functionalization process may be batch, semi-batch or continuous. Asused herein, the term continuous means a system that operates withoutinterruption or cessation. For example, a continuous process to producea polymer would be one where the reactants are continually introducedinto one or more reactors and polymer product is continually withdrawn.

Useful reaction vessels include reactors (including continuous stirredtank reactors, batch reactors, reactive extruder, pipe or pump).

Preferably, the productivity of the functionalization process is atleast 200 g of functionalized polymer per mmol of catalyst per hour,preferably at least 5,000 g/mmol/hour, preferably at least 10,000g/mmol/hr, preferably at least 300,000 g/mmol/hr.

This invention further relates to a process, preferably an in-lineprocess, preferably a continuous process, to produce functionalizedpolymers, comprising introducing one or more monomers into a reactor topolymerize, obtaining a reactor effluent containing polymers, optionallyremoving (such as flashing off) solvent, unused monomer and/or othervolatiles, obtaining the polymer backbone, introducing the polymerbackbone, spacer group, a silane, and a metathesis catalyst into areaction zone (such as a reactor, an extruder, a pipe and/or a pump),obtaining a reactor effluent containing functionalized polymers,optionally removing (such as flashing off) solvent, unused monomerand/or other volatiles, (such as those described herein), and obtainingfunctionalized polymers (such as those described herein). In anembodiment, the spacer group is attached to the silane (via methodsknown in the art) prior to introducing it into the reaction zone withthe polymer backbone and the metathesis catalyst.

Metathesis products prepared herein can further be hydrogenated aftercompletion or during reaction conditions.

The hydrogenation may be achieved in the presence of any of the knowncatalysts commonly used for hydrogenating petroleum resins. Thecatalysts which may be used in the hydrogenation step include the Group10 metals such as nickel, palladium, ruthenium, rhodium, cobalt, andplatinum, and the Group 6 metals such as tungsten, chromium andmolybdenum, and the Group 11 metals such as rhenium, manganese, andcopper. These metals may be used singularly or in a combination of twoor more metals, in the metallic form or in an activated form, and may beused directly or carried on a solid support such as alumina orsilica-alumina. A preferred catalyst is one comprising sulfidednickel-tungsten on a gamma-alumina support having a fresh catalystsurface area ranging from 120 to 300 m²/g and containing from 2% to 10%by weight nickel and from 10% to 25% by weight tungsten as described inU.S. Pat. No. 4,629,766. The hydrogenation is carried out with ahydrogen pressure of 20-300 atmospheres, preferably 150-250 atmospheres.

While the functionalized resins used in the examples in the presentinvention are prepared via metathesis chemistry, in an embodiment of theinvention the resins can be prepared via free radical chemistry and/orhydrosilylation processes known in the art as well.

High Performance Tire Tread Compositions

The functionalized polymer produced by this invention can be used in ahigh performance tire tread composition.

The high performance tire tread composition is formed by blending thefunctionalized polymer produced by this invention with diene elastomerand inorganic filler. Preferably, the functionalized polymer is presentwithin the range from 5 to 100 phr, more preferably 10 to 50 phr, mostpreferably 15 to 50 phr. The diene elastomer may comprise a blend of twoor more elastomers. The individual elastomer components may be presentin various conventional amounts, with the total diene elastomer contentin the tire tread composition being expressed as 100 phr in theformulation. Preferably, the inorganic filler is present within therange from 50 to 150 phr, more preferably 50 to 100 phr, most preferably70 to 90 phr.

Diene Elastomer

As used herein, the term “diene elastomer” is meant to refer to anyviscoelastic polymer synthesized from hydrocarbon monomer comprising twocarbon double bonds.

Examples of preferred diene elastomers include, but are not limited tonatural rubber, polybutadiene rubber, polyisoprene rubber,styrene-butadiene rubber, isoprene-butadiene rubber, highcis-polybutadiene, ethylene-propylene rubber, ethylene-propylene-dienerubber, nitrile rubber, butyl rubber, halogenated butyl rubber, branched(“star-branched”) butyl rubber, halogenated star-branched butyl rubber,poly(isobutylene-co-p-methylstyrene), brominated butyl rubber,chlorinated butyl rubber, star-branched polyisobutylene rubber, andmixtures thereof. Blends of these diene elastomers may be reactor blendsand/or melt mixes. Particularly preferred diene elastomers includepolybutadiene rubber and styrene-butadiene rubber. Preferably, thestyrene-butadiene rubber has a styrene content of 25 wt %. A preferredstyrene-butadiene rubber is commercially available by Lanxess as Buna™VSL 5025-2.

Inorganic Filler

The term “filler” as used herein refers to any material that is used toreinforce or modify physical properties, impart certain processingproperties, or reduce cost of an elastomeric composition.

Examples of preferred filler include, but are not limited to, calciumcarbonate, clay, mica, silica, silicates, talc, titanium dioxide,alumina, zinc oxide, starch, wood flour, carbon black, or mixturesthereof. The fillers may be any size and typically range, for example inthe tire industry, from 0.0001 μm to 100 μm.

As used herein, the term “silica” is meant to refer to any type orparticle size silica or another silicic acid derivative, or silicicacid, processed by solution, pyrogenic, or the like methods, includinguntreated, precipitated silica, crystalline silica, colloidal silica,aluminum or calcium silicates, fumed silica, and the like. Precipitatedsilica can be conventional silica, semi-highly dispersible silica, orhighly dispersible silica. A preferred filler is commercially availableby Rhodia Company under the trade name Zeosil™ Z1165.

Coupling Agent

As used herein, the term “coupling agent” is meant to refer to any agentcapable of facilitating stable chemical and/or physical interactionbetween two otherwise non-interacting species, e.g., between a fillerand a diene elastomer. Coupling agents cause silica to have areinforcing effect on the rubber. Such coupling agents may be pre-mixed,or pre-reacted, with the silica particles or added to the rubber mixduring the rubber/silica processing, or mixing, stage. If the couplingagent and silica are added separately to the rubber mix during therubber/silica mixing, or processing stage, it is considered that thecoupling agent then combines in situ with the silica.

The coupling agent may be a sulfur-based coupling agent, an organicperoxide-based coupling agent, an inorganic coupling agent, a polyaminecoupling agent, a resin coupling agent, a sulfur compound-based couplingagent, oxime-nitrosamine-based coupling agent, and sulfur. Among these,preferred for a rubber composition for tires is the sulfur-basedcoupling agent.

In an embodiment, the coupling agent is at least bifunctional.Non-limiting examples of bifunctional coupling agents includeorganosilanes or polyorganosiloxanes. Other examples of suitablecoupling agents include silane polysulfides, referred to as“symmetrical” or “unsymmetrical” depending on their specific structure.Silane polysulphides can be described by the formula (V)Z-A-S_(x)-A-Z  (V)in which x is an integer from 2 to 8 (preferably from 2 to 5); the Asymbols, which are identical or different, represent a divalenthydrocarbon radical (preferably a C₁-C₁₈ alkylene group or a C₆-C₁₂arylene group, more particularly a C₁-C₁₀, in particular C₁-C₄,alkylene, especially propylene); the Z symbols, which are identical ordifferent, correspond to one of the three formulae (VI):

in which the R¹ radicals, which are substituted or unsubstituted andidentical to or different from one another, represent a C₁-C₁₈ alkyl,C₅-C₁₈ cycloalkyl or C₆-C₁₈ aryl group (preferably C₁-C₆ alkyl,cyclohexyl or phenyl groups, in particular C₁-C₄ alkyl groups, moreparticularly methyl and/or ethyl); the R² radicals, which aresubstituted or unsubstituted and identical to or different from oneanother, represent a C₁-C₁₈ alkoxyl or C₅-C₁₈ is cycloalkoxyl group(preferably a group selected from C₁-C₈ alkoxyls and C₅-C₈cycloalkoxyls, more preferably still a group selected from C₁-C₄alkoxyls, in particular methoxyl and ethoxyl).

International Patent Application Nos. WO 03/002648 and WO 03/002649further disclose silane polysulfides. Non-limiting examples of silanepolysulphides includebis((C₁-C₄)alkoxy(C₁-C₄)alkylsilyl(C₁-C₄)alkyl)polysulphides (inparticular disulphides, trisulphides or tetrasulphides), such as, forexample, bis(3-trimethoxysilylpropyl) orbis(3-triethoxysilylpropyl)polysulphides. Further examples includebis(3-triethoxysilylpropyl)tetrasulphide, abbreviated to TESPT, offormula [(C₂H₅O)₃Si(CH₂)₃S₂]₂, or bis(triethoxysilylpropyl)disulphide,abbreviated to TESPD, of formula [(C₂H₅O)₃Si(CH₂)₃S]₂. Other examplesinclude bis(mono(C₁-C₄)alkoxyldi(C₁-C₄)alkylsilylpropyl)polysulphides(in particular disulphides, trisulphides or tetrasulphides), moreparticularly bis(monoethoxydimethylsilylpropyl)tetrasulphide, such asdescribed in International Patent Application No. WO 02/083782.

The coupling agent can also be bifunctional POSs (polyorganosiloxanes),or hydroxysilane polysulphides, as described in International PatentApplication Nos. WO 02/30939, WO 02/31041 and WO2007/061550, or silanesor POSs bearing azodicarbonyl functional groups, as described inInternational Patent Application Nos. WO 2006/125532, WO 2006/125533 andWO 2006/125534. The coupling agent can also include other silanesulphides, for example, silanes having at least one thiol (—SH)functional group (referred to as mercaptosilanes) and/or at least onemasked thiol functional group, as described in U.S. Pat. No. 6,849,754,and international Patent Nos. WO 99/09036, WO 2006/023815, WO2007/098080, WO 2008/055986 and WO 2010/072685.

The coupling agent can also include combinations of one at more couplingagents described herein, as further described in International PatentApplication No. WO 2006/125534. A preferred coupling agent comprisesalkoxysilane or polysulphurized alkoxysilane. A particularly preferredpolysulphurized alkoxysilane is bis(triethoxysilylpropyl) tetrasulphide,which is commercially available by Degussa under the trade name X50S™.

Plasticizer

As used herein, the term “plasticizer” (also referred to as a processingoil), refers to a petroleum derived processing oil and syntheticplasticizer. Such oils are primarily used to improve the processabilityof the composition. Suitable plasticizers include, but are not limitedto, aliphatic acid esters or hydrocarbon plasticizer oils such asparaffinic oils, aromatic oils, naphthenic petroleum oils, andpolybutene oils. A particularly preferred plasticizer is naphthenic oil,which is commercially available by Nynas under the trade name Nytex™4700.

Antioxidant

As used herein, the term “antioxidant” refers to a chemical that combatsoxidative degradation. Suitable antioxidants includediphenyl-p-phenylenediamine and those disclosed in The Vanderbilt RubberHandbook (1978), Pages 344 to 346. A particularly preferred antioxidantis para-phenylenediamines, which is commercially available by Eastmanunder the trade name Santoflex™ 6PPD.

Crosslinking Agents, Curatives, Cure Packages, and Curing Processes

The elastomeric compositions and the articles made from thosecompositions are generally manufactured with the aid of at least onecure package, at least one curative, at least one crosslinking agent,and/or undergo a process to cure the elastomeric composition. As usedherein, at least one curative package refers to any material or methodcapable of imparting cured properties to a rubber as is commonlyunderstood in the industry. A preferred agent is sulfur.

Processing

The inventive tire tread composition may be compounded (mixed) by anyconventional means known to those skilled in the art. The mixing mayoccur in a single step or in multiple stages. For example, theingredients are typically mixed in at least two stages, namely at leastone non-productive stage followed by a productive mixing stage. Theterms “non-productive” and “productive” mix stages are well known tothose having skill in the rubber mixing art. The elastomers, polymeradditives, silica and silica coupler, and carbon black, if used, aregenerally mixed in one or more non-productive mix stages. Mostpreferably, the polymers are mixed first at 110° C. to 130° C. for 30seconds to 2 minutes, followed by addition of the silica, silica couplerand other ingredients, the combination of which is further mixed, mostpreferably at an increasing temperature up to 140° C. to 160° C. for 30seconds to 3 or 4 minutes. Most desirably the silica is mixed inportions, most preferably one half, then the second half. The finalcuratives are typically mixed in the productive mix stage. In theproductive mix stage, the mixing typically occurs at a temperature, orultimate temperature, lower than the mix temperature(s) of the precedingnon-productive mix stage(s).

Cure Properties

Cure properties were measured using MDR 2000 from Alpha Technologies,Inc. at 160° C. based on ASTM D-2084. “MH” and “ML” used herein refer to“maximum torque” and “minimum torque,” respectively. “Delta Torque” usedherein refers to the difference between MH and ML.

Static Mechanical Properties

Tire tread compositions formed from the functionalized resins of thepresent invention exhibit superior static mechanical properties measuredvia stress/strain analysis in accordance with ISO 37:2011, indicatingimproved durability.

Dynamic Mechanical Properties

Tire tread compositions formed from the functionalized resins of thepresent invention exhibit superior dynamic mechanical propertiesmeasured via dynamic mechanical analysis (DMA) at 100° C., 14% strain,and 5 Hz in accordance with ASTM D7605, indicating improved durability,traction, and handling.

Tan delta at 100° C. can be used as an indicator of tire grip and otherenhanced performance characteristics under extreme use conditions.

EXAMPLES

The ruthenium catalyst used in Example 1 is1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)dichloride.

Example 1 Preparation of DCPD-F

The preparation of functionalized resins according to the presentinvention can be illustrated as follows.

In the glove box, a 100 mL round-bottomed flask was charged with apolymer backbone (Escorez™ E8400 for E1 and E2 and Escorez™ 5415 for C)(10 g), toluene (solvent) (50 mL), and a stir bar. While stirring, thesolution was heated to 60° C. After all of the resin had dissolved, aspacer group functionalized with silane (allyl triethoxysilane (2.88 mL)(for inventive example E2) or hexenyl triethoxysilane (3.56 mL) (forinventive example E1)) was added, followed by the ruthenium catalyst(0.387 g). Comparative example C contains no spacer group and adifferent polymer backbone After stirring at 60° C. for 18 h, themixture was poured into rapidly stirring methanol (300 mL) and filtered.The solids were dried in a vacuum oven at 35° C. for 16 h.

Example 2 Preparation of Tire Tread Compositions C & E1-E2

Comparative tire tread composition C and inventive tire treadcompositions E1-E2 were obtained by first mixing 15 phr of the resintype shown in Table 1 with the ingredients listed in Table 2 (allamounts given in phr) in a Brabender™ mixer. All of the examples, C, E1and E2, contain the same amount and type of diene elastomers, filler,coupling agent, oil, and antioxidant.

This first mix cycle was as follows: 1) mixer rotor speed was set at 25RPM, temperature at 120° C.; all the ingredients were added and the rpmswere adjusted to maintain a batch temperature with the range from151-153° C. for one minute.

TABLE 1 C E1 E2 Resin Type DCPD-H2 DCPD-F DCPD-F Trade Name Escorez ™5415 Escorez ™ 8400 Escorez ™ 8400 Spacer — C₆H₁₀ C₃H₄

TABLE 2 Ingredient Trade Name C E1 E2 Styrene-butadiene Buna ™ VSL5025-2 60 60 60 rubber (elastomer) Silica (filler) Zeosil ™ Z1165 70 7070 Polybutadiene Taktene ™ 1203 40 40 40 (elastomer) PolysulphurizedDegussa X50S 5.6 5.6 5.6 alkoxysilane supported on carbon black(coupling agent) naphthenic oil Nytex ™ 4700 20 20 20 AntioxidantSantoflex ™ 6PPD 2 2 2

The resulting compounds were cooled and then blended using the sameBrabender™ mixer with curatives in the amounts shown in Table 3 (allamounts given in phr). All of the examples, C and E1-E2, contain thesame cure package. This second pass was performed as follows: 1) mixerrotor speed was set at 35 RPM, temperature at 70° C.; 2) add compoundfrom first pass and mix for 30 seconds; 3) add curatives and mix for sixminutes and 30 seconds; and 4) remove batch for a total mixing time ofseven minutes from the addition of the compound.

TABLE 3 C E1 E2 Stearic acid 2.5 2.5 2.5 Zinc oxide 2.5 2.5 2.5 Sulfur1.4 1.4 1.4 (crosslinking agent) Santocure ™ 1.7 1.7 1.7 CBS (rubberaccelerator) Perkacit ™ 2 2 2 DPG (rubber accelerator)

Example 3 Cure Properties and Static Mechanical Properties of C & E1-E2

To determine static mechanical stress/strain properties (tensilestrength, elongation at break, modulus values) of the comparative andinventive materials, compositions C and E1-E2 were first compressionmolded and cured into plaques at 160° C. for t90 (MDR)+5 minutes moldlag time. Dog-bone shaped samples were dried out of these plaques usingBritish standard dies (type 2). Stress/strain measurements were thenperformed in accordance with ISO 37:2011.

The results of these cure and stress/strain measurements are summarizedin Table 4.

TABLE 4 C E1 E2 ML (dNm) 7.6 3.6 4.1 MH (dNm) 31.1 30.0 28.5 DeltaTorque 23.5 26.4 24.4 (dNm) Modulus′ at 686 828 897 200% strain (psi)Ultimate 2223 2277 2191 tensile strength (psi) Ultimate 479 466 444elongation (%)

The inventive materials E1 and E2 show lower ML values compared to thecomparative C, demonstrating improved silica dispersion. E1 and E2 showa larger modulus at 200% than C, demonstrating improved durability. E1and E2 show tensile and elongation values comparable to that of C.

Example 4 Dynamic Mechanical Properties of C & E1-E2

The dynamic mechanical properties of the inventive and comparativematerials, measured at 100° C., are summarized in Table 5.

TABLE 5 C E1 E2 G′ at 14% 1363 1672 1691 (kPa) tan delta at 0.169 0.2430.246 14%

Inventive materials E1 and E2 show a larger G′ at 14% and tan delta at14%, demonstrating improved durability, traction, and handling over thecomparative material C during heavy handling.

INDUSTRIAL APPLICABILITY

The compositions of the invention may be extruded, compression molded,blow molded, injection molded, and laminated into various shapedarticles including fibers, films, laminates, layers, industrial partssuch as automotive parts, appliance housings, consumer products,packaging, and the like.

In particular, the compositions comprising the resin are useful in avariety of tire applications such as truck tires, bus tires, automobiletires, motorcycle tires, off-road tires, aircraft tires, and the like.Such tires can be built, shaped, molded, and cured by various methodswhich are known and will be readily apparent to those having skill inthe art. The compositions may be fabricated into a component of afinished article for a tire. The component may be any tire componenttreads, sidewalls, chafer strips, tie gum layers, other reinforcing cordcoating materials, cushion layers, and the like.

The compositions comprising the resin of the present invention areuseful in a variety of applications, particularly tire curing bladders,inner tubes, air sleeves, hoses, belts such as conveyor belts orautomotive belts, solid tires, footwear components, rollers for graphicarts applications, vibration isolation devices, pharmaceutical devices,adhesives, caulks, sealants, glazing compounds, protective coatings, aircushions, pneumatic springs, air bellows, accumulator bags, and variousbladders for fluid retention and curing processes. They are also usefulas plasticizers in rubber formulations; as components to compositionsthat are manufactured into stretch-wrap films; as dispersants forlubricants; and in potting and electrical cable filling and cablehousing materials.

The compositions comprising the resin may also be useful in moldedrubber parts and may find wide applications in automobile suspensionbumpers, auto exhaust hangers, and body mounts. In yet otherapplications, compositions of the invention are also useful in medicalapplications such as pharmaceutical stoppers and closures and coatingsfor medical devices.

Certain embodiments and features have been described using a set ofnumerical upper limits and a set of numerical lower limits. It should beappreciated that ranges from any lower limit to any upper limit arecontemplated unless otherwise indicated. Certain lower limits, upperlimits, and ranges appear in one or more claims below. All numericalvalues are “about” or “approximately” the indicated value, and take intoaccount experimental error and variations that would be expected by aperson having ordinary skill in the art.

To the extent a term used in a claim is not defined above, it should begiven the broadest definition persons in the pertinent art have giventhat term as reflected in at least one printed publication or issuedpatent. Furthermore, all patents, test procedures, and other documentscited in this application are fully incorporated by reference to theextent such disclosure is not inconsistent with this application and forall jurisdictions in which such incorporation is permitted.

The invention claimed is:
 1. A functionalized resin composition havingthe formula (I)P—S—X  (I) where S is a spacer selected from at least one of C₂-C₄₀straight chain and branched alkyl, C₆-C₄₀ aromatics, butadiene,isoprene, and combinations thereof, P is a polymer backbone selectedfrom at least one of dicyclopentadiene (DCPD)-based polymers,cyclopentadiene (CPD)-based polymers, DCPD-styrene copolymers, C₅homopolymers and copolymer resins, C₅-styrene copolymer resins, terpenehomopolymer or copolymer resins, pinene homopolymer or copolymer resins,C₉ homopolymers and copolymer resins, C₅/C₉ copolymer resins,alpha-methylstyrene homopolymer or copolymer resins, and combinationsthereof, and X is a silane; wherein P, S, and X are contacted in thepresence of a metathesis catalyst to produce the functionalized resincomposition, wherein the metathesis catalyst comprisestricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][3-phenyl-1H-inden-1-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[3-phenyl-1H-inden-1-ylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazol-2-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][(phenylthio)methylene]ruthenium(II)dichloride,bis(tricyclohexylphosphine)-3-phenyl-1H-inden-1-ylideneruthenium(II)dichloride,1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride,[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II)chloride, and fluoride and bromide derivatives thereof, or a mixture ofany of the above.
 2. The functionalized resin composition of claim 1,wherein X is of the formulae

where each Y is independently a nitrogen, oxygen, or sulfur atom, each Zis independently a boron, nitrogen, oxygen, silicon, or sulfur atom,each R is independently a monovalent (for I) or a divalent (for II)substituted or unsubstituted alkyl or aromatic group of from 1 to 20carbon atoms containing at least one olefinic group, each R¹ isindependently a hydrogen atom, or a substituted or unsubstituted alkylor aromatic group of from 1 to 20 carbon atoms, each R² is independentlya divalent substituted or unsubstituted alkyl or aromatic group of from1 to 20 carbon atoms, each R³ is independently a hydrogen atom, ahalogen atom, a substituted or unsubstituted alkyl or aromatic group offrom 1 to 20 carbon atoms, R¹, R², and R³ may form single ormultinuclear rings with each other, where a-f are independently integersof 1, 2, or 3, with the proviso that a+b+c and d+e+f are both equal to3, and where independently for each Y and Z, if Z is a boron atom, thenx=2, if Y or Z is a nitrogen atom, then x=2, if Y or Z is an oxygen atomor sulfur atom, then x=1, if Z is a silicon atom, then x=3; wherein eachR is the spacer S.
 3. The functionalized resin composition of claim 1,wherein P comprises: (i) within the range from 60-100 wt % cycliccomponents; (ii) less than or equal to 15 wt % components derived frompiperylene; (iii) less than or equal to 15 wt % components derived fromamylene; (iv) less than or equal to 15 wt % components derived fromisoprene; (v) less than or equal to 20 wt % components derived fromstyrene; and (vi) less than or equal to 20 wt % components derived fromindene.
 4. A tire tread composition comprising the functionalized resincomposition of claim 1.